Ionized field droplet charging

Figure 3. Effect of spray-liquid dielectric constant upon charging-field concentration factor jj.+2(K-l)/(K+2Q associated with ionized-field droplet charging.

Other Soft Ionization Processes for Large Molecules. Electrospray ionization creates ions by a potential difference between a metal capillary tube and the inlet to the mass spectrometer. The electric field generates charged droplets in the form of a fine mist (see Ref. 25). Application of a drying gas or heat evaporates the solvent, reducing the droplet size and eventually resulting in the formation of molecular ions. 

The term electrospray reveals important features of the process first of all, and differently from the ionization methods described so far, the ionization occurs on a spray. This is produced by forcing a liquid to pass through a capillary, as occurs with perfume dispensers. This causes the formation of millions and millions of small droplets. The first part of the ionization s term contains further important information an electric field (3 5 kV) is applied to the capillary and it causes ionization (Figure 2.3). The overall effect is the formation of small liquid-charged droplets from which gas phase ions are formed. ESI is governed by a large number of chemical and physical parameters that... 

Electrospray ionization (ESI) refers to the overall process by which an intense electric field disperses a sample liquid into a bath gas as a fine spray of highly charged droplets. Evaporation of those charged droplets produces gas-phase ions by mechanisms that remain the subject of much argument and debate. The ESI is a complex of independent component processes, the two most important of which are electrospray dispersion, the electrostatic dispersion of sample liquid into charged droplets, and ionization, the transformation of solute species in those droplets to free ions in the gas phase. 

In IC-MS systems, the core of the equipment is the interface. In fact, inside the interface evaporation of the liquid, ionization of neutral species to charged species and removal of a huge amount of mobile phase to keep the vacuum conditions required from the mass analyzer take place. Two main interfaces are used coupled to IC, namely electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). In the ESI mode, ions are produced by evaporation of charged droplets obtained through spraying and an electrical field, whilst in the APCI mode the spray created by a pneumatic nebulizer is directed towards a heated region (400°C-550°C) in which desolvation and vaporization take place. The eluent vapors are ionized by the corona effect (the partial discharge... 

In ESI MS, a dissolved sample is sprayed through a capillary in an electric field which is situated in front of the vacuum inlet of the mass spectrometer [2]. Thus, in contrast to most other ionization techniques performed in high vacuum, the ionizahon process takes place at the atmospheric pressure. After leaving the capillary, the solvent forms a so-called Taylor-cone, which further forms a filament and finally, the spray of small droplets (Figure 14.2). These droplets carry charges on the surface this is frequently supported by the acidification of the solvent. The droplets shrink is caused by the evaporation of the solvent. This leads to an increase of the charge-per-surface ratio, finally... 

Figure 14.2 Principle of electrospray ionization, (a) The analyte is dissolved in an appropriate solvent and sprayed via a capillary into an electric field. Here, the liquid filament finally forms charged droplets, (b) The solvent of the charged droplets evaporates, resulting in an increase of the surface charge up to a critical boundary, at which a Coulomb explosion occurs. The newly formed droplets undergo the same process. The final products are the desolvated, naked ions, which are then entering the mass spectrometer.

A practical application coming out of field ion emission is the liquid metal ion source. Ion sources of a wide variety of chemical elements, most of them low melting point metals, can be produced by using either liquid metals131,132 or liquid alloys.133 The idea of extracting charged droplets out of liquid by application of an electrostatic field is perhaps older than field ion microscopy. But the development of liquid metal ion sources from liquid capillaries, from slit shaped emitter modules and from wetted field emission tips, etc., as well as the understanding of the mechanisms of ion formation in terms of field evaporation and field ionization theories,... 

Electrospray ionization involves the introduction of a liquid solution directly into the atmospheric pressure source through an emitter. The liquid forms a droplet at the end of the emitter, where it is exposed to a high electrical field (Fig. 1). This results in a buildup of multiple charges on the surface of the droplet. The coulombic forces from these charges ultimately result in the droplet s expulsion from the surface. The ions produced in the ion source are then extracted into the mass analyzer. ESI is now widely used for identifying small molecules, proteins, studying large non-covalent complexes, structural analysis, and as a detector for separation methods such as HPLC and capillary... 

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